CN111545224A - Up-conversion photocatalytic material and preparation method and application thereof - Google Patents
Up-conversion photocatalytic material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 71
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 241000894006 Bacteria Species 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 63
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 34
- 230000001954 sterilising effect Effects 0.000 claims description 23
- 238000004659 sterilization and disinfection Methods 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 229910009523 YCl3 Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 229910019328 PrCl3 Inorganic materials 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
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- 239000007787 solid Substances 0.000 claims description 7
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
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- 238000001816 cooling Methods 0.000 claims description 6
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- 239000000594 mannitol Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910002637 Pr6O11 Inorganic materials 0.000 claims description 4
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- 230000035484 reaction time Effects 0.000 claims description 4
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000002060 nanoflake Substances 0.000 claims description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 241000588724 Escherichia coli Species 0.000 abstract description 6
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 241000192125 Firmicutes Species 0.000 abstract description 2
- -1 free radical compound Chemical class 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000000249 desinfective effect Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
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- 150000003254 radicals Chemical class 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
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- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 229910003366 β-NaYF4 Inorganic materials 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to an up-conversion photocatalytic material β -NaYF4:Pr3+,Li+@ BiOCl, its ultraviolet ray that can launch UVC wave band just can effectively reduce combined material's forbidden bandwidth, increases the photoresponse range, realizes the effect that ultraviolet light and active free radical compound disinfect, improves the efficiency of disinfecting. According to the preparation method, the up-conversion material is synthesized by a hydrothermal method, the BiOCl photocatalyst is modified by the up-conversion material, and the up-conversion photocatalytic material is synthesized by a two-step hydrothermal method. The method of the invention is simpleSimple and easy to operate. The up-conversion catalyst provided by the invention has good bactericidal effect on gram-negative bacteria (such as escherichia coli) and gram-positive bacteria (such as staphylococcus aureus).
Description
Technical Field
The invention belongs to the field of sterilization of photocatalytic materials, and particularly relates to an up-conversion photocatalytic material and a preparation method and application thereof.
Background
The up-conversion photocatalytic material is a novel material capable of being used for eliminating pathogenic bacteria, and is formed by compounding rare earth ions with up-conversion luminescence function and a photocatalytic material. Upconverters enable the conversion of visible light to ultraviolet light due to their unique upconversion characteristics. Meanwhile, the photocatalytic material can generate active species with strong oxidation reduction property by utilizing light energy, has no obvious selectivity when treating microbial pollution, can efficiently kill microorganisms, has good stability, and shows good application prospect as a sterilization material.
CN 1087224507 discloses a preparation method of an up-conversion phosphor composite photocatalytic material based on high-intensity ultraviolet emission. The method comprises the steps of firstly preparing high-strength ultraviolet-emitting up-conversion fluorescent powder by taking rare earth oxide as a raw material, and then compounding the prepared fluorescent powder with TiO to prepare the TiO-coated high-strength ultraviolet-emitting up-conversion fluorescent powder composite photocatalytic material. The prepared up-conversion phosphor powder composite photocatalytic material based on high-intensity ultraviolet emission utilizes the up-conversion material to absorb near infrared light for conversion to emit strong ultraviolet light, then excites TiO and generates catalytic activity to realize the utilization of the near infrared light, widens the response range of photocatalysis to solar spectrum, has high dispersion, is non-toxic and harmless, and meets the requirement of environmental protection. The material is prepared by a hydrothermal method, the preparation process is simple and easy to operate, the cost is reduced to a certain extent, and the material is particularly suitable for batch production and can be applied to the field of photocatalytic environment treatment. But the emitted fluorescence spectra are all larger than 300nm, and the sterilization effect is limited (the ultraviolet sterilization effect of UVC wave band is the most excellent).
Disclosure of Invention
The invention aims to overcome the defects and provide an up-conversion photocatalytic material and a preparation method and application thereof. The up-conversion photocatalytic material can emit ultraviolet light in UVC wave band, effectively reduce the forbidden bandwidth of the composite material, increase the photocatalytic efficiency, realize the composite sterilization effect of ultraviolet light and active free radicals, and improve the sterilization efficiency.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an up-conversion photocatalytic material is characterized in that the material is β -NaYF4:Pr3+,Li+@ BiOCl (abbreviated as NYF-Bi).
Preferably, the up-conversion photocatalytic material is of a core-shell structure, and the core is β -NaYF of hexagonal prism solid crystal4:Pr3+,Li+The diameter is 2-3 μm, and the height is 3-5 μm; the shell is uniformly distributed on the NaYF4:Pr3+The length and width of the BiOCl nano-flake on the surface are both 50-150 nm.
A preparation method of an up-conversion photocatalytic material is characterized by comprising the following steps:
(1) to uniform dispersion of YCl3、PrCl3Adding EDTA into a mixed hydrochloric acid solution of LiCl, stirring, adding a NaF solution, adjusting the pH value to be alkaline to form a solution A by ammonia water, transferring the solution A to a reaction kettle after vigorous stirring, reacting for 20-28 h at the temperature of 150-250 ℃, cooling, washing the solid, and drying to obtain an up-conversion material β -NaYF4:Pr3+,Li+(abbreviated NYF);
(2) adding Bi (NO)3)3Or dissolving the crystal hydrate in mannitol, adding saturated NaCl solution to form suspension, and adding the up-conversion material β -NaYF prepared in step (1)4:Pr3+,Li+Stirring to form a solution B, transferring the solution B to a reaction kettle, reacting for 2-5 hours at the temperature of 100-150 ℃, separating, washing and drying to obtain the up-conversion photocatalytic material β-NaYF4:Pr3+,Li+@BiOCl。
Preferably, the mixed hydrochloric acid solution is prepared from YCl3Solution, PrCl3Mixing the solution with LiCl solution to obtain YCl3Solution, PrCl3Solution and LiCl solution, respectively from Y2O3，Li2O，Pr6O11Dissolving in hydrochloric acid solution.
Preferably, in the step (1), YCl is added to the mixed hydrochloric acid solution3、PrCl3The mass ratio of the LiCl to the LiCl is 200 to (2.8-3.2) to (17.8-18.2). Preferably, in step (1), YCl3The mass ratio of NaF to NaF was 9: 2.
Preferably, in step (1), the concentration of EDTA in the solution A is 0.025 mol/L.
Preferably, in step (1), said YCl3Solution, PrCl3The concentration of the solution and the concentration of the LiCl solution are both 0.05-0.15 mol/L. Preferably, the concentration of the NaF solution is 0.4-0.6 mol/L.
Preferably, in the step (1), the pH is adjusted to 8.5-9.0, and the vigorous stirring time is 50-70 min.
Preferably, in the step (1), the reaction temperature is 190-210 ℃, and the reaction time is 23-25 h.
Preferably, in step (2), Bi (NO)3)3The mass ratio to upconverting material was 0.374: 1.
Preferably, in step (2), Bi (NO)3)3The concentration of the solution after being dissolved in the mannitol aqueous solution is 0.03-0.05 mol/L.
Preferably, in the step (2), the reaction temperature is 110-130 ℃, and the reaction time is 2.8-3.2 h.
The application of the up-conversion photocatalytic material in the sterilization field also belongs to the protection scope of the invention, preferably, the application method is to throw the up-conversion photocatalytic material into the water body needing sterilization and sterilize in the illumination environment, preferably, the adding amount in the water body is 0.15g/L, the bacteria concentration in the water body is 0.9 × 106～1.1×106CFU/mL。
The invention has the beneficial effects that:
(1) NYF in the up-conversion photocatalytic material can convert light within the range of 200-1000 nm into ultraviolet light at UVC (200-280 nm), the part of ultraviolet light can excite BiOCl in the up-conversion photocatalytic material to generate active groups and can further sterilize, and the ultraviolet light at a specific waveband has an excellent effect on sterilization; the up-conversion photocatalytic material not only provides absorbable ultraviolet light for BiOCl, but also reduces the forbidden bandwidth of BiOCl to 2.95ev, the excitation spectrum range of the BiOCl is expanded from less than 354nm to less than 420nm by external light, and the excitation spectrum range is expanded from the ultraviolet light wave band to a part of visible light range, so that the efficiency of exciting and generating active free radicals is improved; therefore, the up-conversion photocatalytic material not only realizes the composite sterilization of ultraviolet sterilization and active free radical sterilization, but also improves the catalytic efficiency of the up-conversion photocatalytic material;
(2) the preparation method is simple and easy to operate, the up-conversion photocatalyst can be successfully prepared, and the prepared up-conversion photocatalyst has high purity and good crystal form.
Drawings
FIG. 1 is an XRD diffraction pattern of NYF-Bi prepared in example 1;
FIG. 2 is SEM and TEM images of NYF-Bi prepared in example 1, wherein a and b are NYF SEM and TEM images, respectively, and c and d are NYF-Bi SEM and TEM images, respectively;
FIG. 3 is a TEM-EDS line scan result chart of NYF-Bi prepared in example 1, wherein a is a schematic view of a line scan region, b is a TEM image of NYF-Bi, c is a line scan content variation chart of Bi element, and d is a line scan content variation chart of Y element;
FIG. 4 is a TEM-EDS surface scan of NYF-Bi prepared in example 1, wherein: (a) NYF-Bi face scan region; (b-h) element distribution diagram of Na, Y, F, Pr, Bi, O, Cl; (i) mass distribution maps of the elements;
FIG. 5 is a graph showing the UV-VIS diffuse emission spectrum of NYF-Bi prepared in example 1;
FIG. 6 is a fluorescence spectrum of NYF-Bi prepared in example 1 in the UVC band with an excitation wavelength of 444 nm;
FIG. 7 is a graph showing the sterilization efficiency in example 3, wherein the object to be sterilized in a is Staphylococcus aureus and b is Escherichia coli;
FIG. 8 is a graph showing the bactericidal efficiency in the case of example 3 in which coexisting ions were present, wherein the coexisting ions in a were 0.9% Na2SO4And the coexisting ion of b is 0.9% NaNO3。
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
The raw materials and equipment used in the invention can be obtained from the market or are commonly used in the field if not specified, and the methods in the examples are conventional in the field if not specified.
Example 1
Step 1: 2.2581g, 0.2988g and 1.0214g of Y were weighed out separately2O3，Li2O，Pr6O11Dissolving in 100mL hydrochloric acid solution to obtain 0.1mol/L YCl30.1mol/L LiCl and 0.01mol/L YCl3LiCl and PrCl3Dissolving 2.0996g NaF in 100mL deionized water to prepare 0.5 mol/L NaF solution;
step 2: respectively taking 40mL, 3.6mL and 6mL YCl3、PrCl3Mixing with LiCl and stirring well, adding 0.292g EDTA, stirring for 30 minutes, adding 18mL NaF solution, adding NH3·H2Regulating the pH value to 8.7 by using O, and then violently stirring to obtain a solution A;
and step 3: and transferring the solution A into a 100mL hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a 200 ℃ oven for reaction for 24 hours, naturally cooling to room temperature after the reaction is finished, then alternately cleaning the solution with absolute ethyl alcohol and deionized water for 3 times, and finally placing the obtained solid in a 60 ℃ oven for drying to obtain the up-conversion material NYF.
And 4, step 4: 0.4861g of Bi (NO)3)3·5H2Dissolving O in 25mL of 0.1mol/L mannitol, adding 5mL of saturated NaCl solution after completely dissolving to form a suspension, and then, adding 1.3g of the upconverting material β -NaYF prepared in step 34:Yb3 +,Li+Adding the aboveStirring and mixing the suspension evenly to obtain solution B;
and 5: the solution B was transferred to a 50mL reaction vessel and placed in a 120 ℃ constant temperature drying oven for 3 hours. And naturally cooling to room temperature after the reaction is finished, performing centrifugal separation, alternately washing for 3 times by using ultrapure water and ethanol, and then placing the sample in a 60 ℃ oven for 8 hours for drying to prepare the NYF-Bi core-shell photocatalytic material.
First, NYF-Bi prepared in example 1 and NYF prepared in example 1 were subjected to XRD diffraction, and the results are shown in FIG. 1. from the XRD pattern peaks of the samples are good, NYF prepared was compared with JCPDS 16-0334 (hexagonal phase β -NaYF)4) As can be seen by comparison, NYF shows obvious diffraction peaks at the positions of 17.2 degrees, 30.1 degrees, 30.8 degrees, 39.7 degrees, 43.5 degrees, 53.3 degrees and 53.8 degrees, and the diffraction peaks are sharp in peak shape, have no impurity peaks and just can be matched with β -NaYF-hexagonal phase4The crystal faces of (100), (110), (101), (111), (201), (300) and (211) are in one-to-one correspondence, which shows that the high-purity hexagonal phase β -NaYF with good crystal form is successfully synthesized4NYF-Bi was compared with a standard card JCPDS 16-0334 (hexagonal phase β -NaYF)4) As compared with JCPDS 06-0249(BiOCl), NYF-Bi can not only be compared with β -NaYF4The diffraction peaks at the positions of 12.0 degrees, 25.9 degrees, 32.5 degrees, 33.4 degrees, 40.9 degrees, 49.7 degrees, 58.6 degrees, 60.5 degrees and the like can also correspond to the crystal planes (001), (101), (110), (102), (112), (113), (212) and (114) of BiOCl one by one, and no impurity peak exists. The hydrothermal synthesis method adopted in the method can well synthesize the composite material NYF-Bi with good crystal form and high crystallinity, and does not change the crystal forms of the two materials.
Then, the NYF-Bi material prepared in example 1 and NYF prepared therein are subjected to electron microscope scanning, and the result is shown in FIG. 2, wherein a and b are SEM and TEM patterns of NYF respectively, and c and d are SEM and TEM patterns of NYF-Bi respectively. As can be seen from the figure, the synthesized NYF exhibited regular hexagonal prism-like solid crystals with smooth surfaces, a diameter of about 2-3um and a height of about 3-5 um. NYF-Bi is also in a hexagonal prism shape and has a size similar to NYF, BiOCl loaded on the surface of the NYF material is in a two-dimensional sheet shape, the length and the width are about 0.1um, and the BiOCl is uniformly wrapped on the surface of the NYF hexagonal prism shape, so that the two-dimensional photocatalytic material NYF-Bi synthesized by a hydrothermal method is in a core-shell structure.
To further verify that the prepared NYF-Bi has a core-shell structure and is subjected to TEM-EDS line scanning, the results are shown in FIG. 3, wherein a is a schematic diagram of a line scanning region, b is a TEM diagram of NYF-Bi, c is a diagram of a change in line scanning content of a Bi element, and d is a diagram of a change in line scanning content of a Y element, and a change trend of contents of two elements, namely a Y element and a Bi element, in the up-conversion photocatalytic material NYF-Bi is recorded on the basis of white lines in a comparison between c and d, it can be found that the scanning process is slowly transferred from the shell structure BiOCl to the core structure β -NaYF from 0-1.0um4Above, Bi element is more and Y element is less, between 1-2.5um, the scanning process is mainly in the nuclear structure β -NaYF4Above, Bi element is reduced and Y element is increased, between 2.5-3um, scanning through the nuclear structure β -NaYF4Continuously moving to a shell structure BiOCl, wherein the Bi element begins to increase and the Y element begins to decrease; it can be shown that the BiOCl on the surface is uniformly loaded on the surface of the hexagonal prism NYF, and the successful combination of the BiOCl as a shell on the surface of the up-conversion material NYF is confirmed to be in a core-shell structure.
Meanwhile, an SEM-EDS (scanning Electron microscope-diffraction system) -surface scanning map is carried out on NYF-Bi, the result is shown in figure 4, and the synthesized composite photocatalytic material contains seven elements of Na, Y, F, Pr, Bi, O and Cl which are uniformly distributed on the surface of the hexagonal prism NYF, and the uniform distribution of the elements of Bi, O and Cl can indicate that BiOCl on the surface is uniformly loaded on the surface of the hexagonal prism NYF, so that the situation that the BiOCl is successfully compounded on the surface of the upper conversion material NYF as a shell to form a core-shell structure is further confirmed.
In order to verify the light absorption and emission of the up-conversion photocatalytic material of the present invention, an ultraviolet-visible diffuse emission spectrogram and an emission spectrogram in the UVC band were performed. Wherein, fig. 5 is an ultraviolet-visible diffuse emission spectrogram of NYF-Bi, and the spectrum result shows that pure BiOCl absorbs light at about 360nm, the absorbance of NYF-Bi after NYF recombination at an ultraviolet band is obviously enhanced, and the forbidden bandwidth of the composite material is reduced from 3.42eV to 2.95eV, so that the material can excite the composite material to generate active radicals in a visible light range. FIG. 6 shows the fluorescence spectra of NYF and NYF-Bi, from which it can be seen that there are three main emission peaks in the ultraviolet range, 253nm, 259nm and 284nm, respectively, illustrating that the prepared upconverting material is capable of converting light of 444nm wavelength in the visible light to light of UVC wavelength. Among them, the emission peak at 284nm has the strongest fluorescence intensity because the wavelength is closer to the used excitation wavelength of 444 nm. Compared with the composite photocatalytic material and the up-conversion material, the emission peak intensity ratio NYF of NYF-Bi is obviously weakened, which shows that NYF of the up-conversion photocatalytic material absorbs visible light and converts the visible light into ultraviolet light to emit out, and the emitted ultraviolet light is absorbed by the photocatalytic material BiOCl compounded on the surface of the hexagonal phase NYF to generate a photocatalytic effect, so that the fluorescence intensity is obviously weakened.
Example 2
Step 1: 2.2585g, 0.2991g and 1.0218g of Y were weighed out separately2O3，Li2O，Pr6O11Dissolving in 100mL hydrochloric acid solution to obtain 0.1mol/L YCl30.1mol/L LiCl and 0.01mol/L YCl3LiCl and PrCl3Dissolving 2.0995g NaF in 100mL deionized water to prepare 0.5 mol/L NaF solution;
step 2: respectively taking 40mL, 3.6mL and 6mL YCl3、PrCl3Mixing with LiCl and stirring well, adding 0.292g EDTA, stirring for 30 minutes, adding 18mL NaF solution, adding NH3·H2Regulating the pH value to 8.8 by using O, and then violently stirring to obtain a solution A;
step 3, transferring the solution A into a 100mL hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a 200 ℃ oven for reaction for 24 hours, naturally cooling the solution to room temperature after the reaction is finished, then alternately cleaning the solution with absolute ethyl alcohol and deionized water for 3 times, and finally placing the obtained solid in a 60 ℃ oven for drying to obtain the up-conversion material β -NaYF4:Pr3+,Li+。
And 4, step 4: 0.4862g of Bi (NO)3)3·5H2Dissolving O in 25mL of 0.1mol/L mannitol, adding 5mL of saturated NaCl solution after completely dissolving to form a suspension, and then adding 1.3g of the upconverting material β -NaYF prepared in step 34:Yb3 +,Li+Adding the suspension, stirring and mixingUniformly obtaining a solution B;
and 5: the solution B was transferred to a 50mL reaction vessel and placed in a 120 ℃ constant temperature drying oven for 3 hours. And naturally cooling to room temperature after the reaction is finished, performing centrifugal separation, alternately washing for 3 times by using ultrapure water and ethanol, and then placing the sample in a 60 ℃ oven for 8 hours for drying to prepare the NYF-Bi core-shell photocatalytic material.
Example 3
The NYF-Bi, NYF prepared in example 1 and commercial BiOCl were subjected to sterilization efficiency tests (all sterilization tests were performed under visible light), wherein the light intensity was 141500 lux and the amount of material added was 0.15 g/L; coexisting ions: 0.9% Cl-(ii) a Initial concentration C of bacterial liquid0：106CFU/mL。
The results are shown in fig. 7, and compared with the bacterial suspension concentration of the blank experiment group, the bactericidal effects of the prepared bactericidal materials NYF and NYF-Bi on two different bacteria are greatly improved, which indicates that the prepared bactericidal materials can achieve better bactericidal effects. Meanwhile, the prepared sterilization material has universality in sterilization effect, and can obtain good sterilization effect no matter gram-negative bacteria (such as escherichia coli, the sterilization rate is 99.999%) or gram-positive bacteria (such as staphylococcus aureus, the sterilization rate is 99.996%).
In order to investigate the application range of the prepared bactericidal material and investigate the bactericidal efficiency of different materials in the presence of common coexisting ions, NYF-Bi, NYF prepared in example 1 and commercial BiOCl were taken to perform bactericidal efficiency measurement in the presence of coexisting ions. Respectively at 0.9% Na2SO4(FIG. a) and 0.9% NaNO3FIG. 8 shows the results of the measurement of the bactericidal efficiency against E.coli in the presence of the reagent (FIG. b). As can be seen from the figure, in the blank experiment of different anions, the concentration of the bacterial suspension of the Escherichia coli is not obviously reduced, which indicates that the existence of the anions does not influence the survival rate of the Escherichia coli, and SO4 2-And NO3 -The existence of (2) has little influence on the sterilization effect of the material. Shows that the material has wide application range and can still keep good in the presence of common anionsGood sterilization efficiency.
Claims (10)
1. An up-conversion photocatalytic material is characterized in that the material is β -NaYF4:Pr3+,Li+@BiOCl。
2. The up-conversion photocatalytic material according to claim 1, wherein the up-conversion photocatalytic material has a core-shell structure, and the core is β -NaYF (NaYF) with a hexagonal solid prism crystal4:Pr3+,Li+The diameter is 2-3 μm, and the height is 3-5 μm; the shell is uniformly distributed on the NaYF4:Pr3+The length and width of the BiOCl nano-flake on the surface are both 50-150 nm.
3. A method for preparing an up-conversion photocatalytic material according to claim 1 or 2, characterized by comprising the steps of:
(1) to uniform dispersion of YCl3、PrCl3Adding EDTA into a mixed hydrochloric acid solution of LiCl, stirring, adding a NaF solution, adjusting the pH value to be alkaline to form a solution A by ammonia water, transferring the solution A to a reaction kettle after vigorous stirring, reacting for 20-28 h at the temperature of 150-250 ℃, cooling, washing the solid, and drying to obtain an up-conversion material β -NaYF4:Pr3+,Li+(abbreviated NYF);
(2) adding Bi (NO)3)3Or dissolving the crystal hydrate in mannitol, adding saturated NaCl solution to form suspension, and adding the up-conversion material β -NaYF prepared in step (1)4:Pr3+,Li+Stirring to form a solution B, transferring the solution B to a reaction kettle, reacting for 2-5 hours at the temperature of 100-150 ℃, separating, washing and drying to obtain the up-conversion photocatalytic material β -NaYF4:Pr3+,Li+@BiOCl。
4. The method according to claim 3, wherein, in the step (1), YCl is contained in the mixed hydrochloric acid solution3、PrCl3The mass ratio of LiCl to LiCl is 200 to (2.8-3.2) to (17.8-18.2); preferably, in step (1), YCl3The mass ratio of NaF to NaF was 9: 2.
5. The process according to claim 3 or 4, wherein in the step (1), the concentration of EDTA in the solution A is 0.025 mol/L.
6. The method of claim 3, wherein the mixed hydrochloric acid solution is prepared from YCl3Solution, PrCl3Mixing the solution with LiCl solution to obtain YCl3Solution, PrCl3Solution and LiCl solution, respectively from Y2O3，Li2O，Pr6O11Dissolving in hydrochloric acid solution to obtain; preferably, in step (1), said YCl3Solution, PrCl3The concentration of the solution and the concentration of the LiCl solution are both 0.05-0.15 mol/L; preferably, the concentration of the NaF solution is 0.4-0.6 mol/L; preferably, in the step (1), the pH is adjusted to 8.5-9.0, and the vigorous stirring time is 50-70 min.
7. The preparation method according to claim 3 or 4, wherein in the step (1), the reaction temperature is 190-210 ℃ and the reaction time is 23-25 h.
8. The production method according to claim 3 or 4, wherein in the step (2), Bi (NO)3)3The mass ratio of the up-conversion material to the up-conversion material is 0.374: 1; preferably, in step (2), Bi (NO)3)3The concentration of the solution after being dissolved in the mannitol aqueous solution is 0.03-0.05 mol/L.
9. The preparation method according to claim 3 or 4, wherein in the step (2), the reaction temperature is 110-130 ℃ and the reaction time is 2.8-3.2 h.
10. The use of the up-conversion photocatalytic material according to claim 1/2 or the up-conversion photocatalytic material prepared by the preparation method according to any one of claims 3 to 9 in the field of sterilization; preferably, the method of application is toThe up-conversion photocatalytic material is put into a water body to be sterilized and is sterilized in a light environment, preferably, the adding amount of the up-conversion photocatalytic material in the water body is 0.15g/L, and the concentration of bacteria in the water body is 0.9 × 106～1.1×106CFU/mL。
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